Benzene diazonium salts useful in diazotype materials having ortho carboxamido substitution



United States Patent 3,463,639 BENZENE DIAZONIUM SALTS USEFUL IN DIAZO-TYPE MATERIALS HAHNG ORTHO CARBOX- AMIDO SUBSTITUTION Evan S. Baltazzi,Brookfield, Ill., assignor to Addressograph-Multigraph Corporation,Mount Prospect, 111., a corporation of Delaware N0 Drawing. Filed Dec.15, 1965, Ser. No. 514,130 Int. Cl. G03c 1/54; C07c 113/04 US. Cl. 96919 Claims ABSTRACT OF THE DISCLOSURE A benzene diazoniurn salt having acarboxamido substituent in the 2-position, a heterocyclic tertiary aminoresidue to the 4-position, and a substituent other than hydrogen in the-position. A typical diazonium salt of this invention is one derivedfrom a 2-(N,N-di-n-butylcarboxamido-4-morpholino-5-methoxybenzenediazonium compound. These diazonium saltsfind utility in both one and two component diazotype materials.

This invention relates to new organic compounds. More particularly, itrelates to derivatives of substituted orthoamino 'benzoic acids whichcan be diazotized to yield light sensitive diazonium salts, and themethod of preparing same.

The compounds of this invention can be illustrated by the followingstructural formulas:

wherein A represents alkoxyl, aroxyl, acyloxyl, hydroxyl, halogen,alkyl, aryl or aralkyl; B is a secondary amine residue; and R is loweralkyl, cycloalkyl, aryl, aralkyl or lower alkyl-substituted heterocyclicradical; R is alkyl, cycloalkyl, aryl or aralkyl; and

is a saturated cyclic amino radical derived from aziridine, pyrrolidine,lower alkyl-substituted pyrrolidine, piperidine, lower alkyl-substitutedpiperidine, hexamethyleneimine, azabicyclononane, piperazine, loweralkyl-substituted piperazine, morpholine and lower alkyl-substitutedmorpholine.

It is an object of this invention to provide new substitutedo-aminobenzamides which are useful in the production of light-sensitivediazonium salts. It is a further object to provide new diazonium saltsuseful in light-sensitive diazotype materials. Another object is toprovide efficient methods for the production of such substitutedo-aminobenzamides and light-sensitive diazonium salts. These and otherobjects are apparent from and achieved in accordance with the followingdetailed disclosure.

In the compounds of the foregoing formulas, A can represent alkoxylgroups such as methoxyl, ethoxyl, propoxyl, butoxyl and pentoxyl.Substituted alkoxyl groups are also suitable, such as ethoxyethoxyl,'butoxybutoxyl 3,463,639 Patented Aug. 26, 1969 and phenoxyethoxyl. Acan also represent aroxyl radicals containing 6 to 10 carbon atoms suchas phenoxyl, toloxyl, xyloxyl, ethylphenoxyl, butylphenoxyl and thelike, as well as acycloxyl, radicals such as acetoxyl, propionoxylbutyroxyl, and the like. Halogens such as fluorine, chlorine and bromineare also represented by A. Alkyl radicals containing 1 to 5 carbonatoms, inclusive, aryl radicals containing 6 to 10 carbon atoms,inclusive, and aralkyl radicals containing 7 to 10 carbon atoms,inclusive, are also within the meaning are the substituent A. Among sucharyl and aralkyl radicals are benzyl, phenethyl, tolylmethyl,phenylbutyl, xylylethyl and the like.

The secondary amino radical represented by B can be dialkylamino radicalsuch as dimethylamino, dipropylamino, methylethylamino,methylpentylamino, ethylbutylamino, methylbenzylamino,ethylbenzylarnino, methylphenethylamino, dibenzylamino, and similarsecondary amino radicals containing 2 to 12 carbon atoms. Heterocyclicamino radicals of the type shown in the examples are preferred.

The radical R can be an alkyl radical containing 1 to 5 carbon atoms,inclusive, a cycloalkyl radical such as cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl and cycloactyl or an aryl oraralkyl radical of the type described above with reference tosubstituent A.

The radical R represents alkyl, cycloalkyl, aryl or aralkyl radicals ofthe type described above.

The compounds of the present invention can be diazotized by conventionaltechniques to yield stable light-sensitive diazonium salts suitable inlight-sensitive coatings that may be applied to substrates such aspaper, cloth or film to form light-sensitive diazotype materials. Thediazonium salts are soluble in water and a spectral analysis of thesematerials exhibits peak absorptions in the range of 400 to 450millimicrons. In this range of spectral sensitivity the diazotypematerials derived from the amines of this invention can be processedmuch faster on existing diazo copying equipment and have led tosimplified copying apparatus equipped with less expensive energy sourcessuch as fluorescent and incandescent light sources.

The compounds of this invention can be prepared by reacting a2-nitro-4-substituted-S-halobenzoyl halide with a secondary alkyl, aryl,aralkyl, or alicyc-lic amine to yield a2-nitro-4-substituted-S-halobenzamide, which is reacted with a secondaryamine and the resulting aminonitrobenzamide reduced to the correspondingdiamonibenzamide. The substituent in the 5-position of the: startingbenzoyl halide corresponds to the radical B described above.

Reaction diagram:

Amine (BE) A 0 S0012 A 0 R1 Secondary l -hon N EN \R2 N02 NO:

A 1 1-1, A R1 Diazotization l I N\ N\ R2 R2 N02 NH:

El) /Ri CN\ 1 2 +2 Referring to the reaction diagram, the secondaryamine can be a compound having from 2 to 12 carbon atoms which is cyclicor acyclic chain.

Typical compounds prepared by the process of this invention include:

N (2-amino-4-methoxy-5-morpolinobenzoyl)-di-n-butylamine N(2-amino-4-methoxy-5-hexamethyleneiminobenzoyl)- di-isobutylamine N (2amino-4-methoxy-S-morpholinobenzoyl)-3-azabicyclo[3.2.2]nonane N2-amino-4-methoxy-5-piperidinobenzoyl hexamethyleneimine N ethyl-N-(2amino-4-methoxy-5-pyrrolidinobenzoyl) aniline N-2-amino-4-rnethoxy-5-piperidinobenzoyl mo-rpholine N methyl-N-(Z-amino 4methoxy 5 hexamethyleneiminobenzoyl)tetrahydrofurfurylamineN-(2-amino-4-methoxy 5 pyrrolidinobenzoyl)pyrrolidineN-(2-amino-4-methoxy-5-pyrrolidinobenzoyl)piperidine N(2-amino-4-methoxy-5-hexamethyleneiminobenzoyl)- 2',6-dimethylpiperidineN (2-amino-4-methoxy-5-hexamethyleneiminobenzoyl)- dicyclohexylamine N(2 amino-4-methoxy-5-pyrrolidinobenzoyl)diphenylamine N isopropyl-N-(Zamino-4-methoxy-S-pyrrolidinobenzoyl)benzylamine N(2-amino-4-butoxy-5-morpholinobenzoyl)-di-isobutylamine N isopropyl-N-(Zamino-4-hydroxy-5-morpholinobenzoyl) benzylamine N isopropyl N(2-amino-4-acetoxy-5-morpholinobenzoyl)benzylarnine N isopropyl-N-(2amino-4-ethoxyethoxy-5-morpho1inobenzoyl)benzylamine Nethyl-N-(2-amino-4-phenoxyethoxy-S-morpholinobenzoyl)aniline N sec.butyl-N-(2 amino 4 chloro-S-hexarnethyleneiminobenzoyl)anilineN-(Z-amino 4 chloro-5-piperidinobenzoyl)-di-isobutylamine.

EXAMPLE 1 Preparation of N-(2-amino-4-methoxy-5-morpholinobenzoyl)-di-n-butylamine One hundred grams (0.43 mole) of 2-nitro-4-methoxy-5-chlorobenzoic acid (prepared by oxidation of 2-nitro-4-methoxy-5-chlorotoluene) was added to a mixture of 200 ml. of benzeneand 200 ml. of thionyl chloride and the reaction mixture heated underreflux for 2 hours. The solution was evaporated and the residue wasdissolved in methylene chloride (250 ml.) and cooled to 0 C. To thissolution, maintained between -15 C., was added with stirring over a10-minute period a solution of di-nbutylamine 125 g.) in methylenechloride (100 ml.). The solution was further stirred while at roomtemperature for 30 minutes. The solution was then washed with dilutehydrochloric acid and twice with water. The solution was evaporated,leaving a residue of N,N-di-n-butyl-2-nitro-4- methoxy-5-chlorobenzamidewhich was recrystallized from petroleum ether; M.P. 72-75 C.

The N,N di-n-butyl-2-nitro-4-methoxy-5-chlorobenzamide (100 g.) wasadded to morpholine (1 liter) and the solution heated on a steam bathfor hours. The solution was concentrated under reduced pressure and theresidue dissolved in methylene chloride, washed with dilute hydrochloricacid and twice with water. The solution was evaporated to a residue ofN,N-di-n-butyl-2-nitro-4- methoxy-S-morpholinobenzamide which wasrecrystallized from petroleum ether; M.P. 64-68" C.

The N,N di-n-butyl-2-nitro-4-methoxy-5-morpholinobenzamide (50 g.) wasdissolved in isopropyl alcohol (400 ml.) and the solution reduced on aParr hydrogenation apparatus at 3-4 atmospheres in the presence of Raneynickel until hydrogen uptake ceased. The mixture was filtered to removethe catalyst, the filtrate concentrated to a residue ofN,N-di-n-butyl-2-amino-4-rnethoxy-5-morpholinobenzamide. It wasrecrystallized from petroleum ether; M.P. 54-56 C.

EXAMPLE 2 Preparation of N-isopropyl-N-(2-amino-4-hydroxy-5-morpholinobenzoyl)benzylamine Preparation ofN-isopropyl-N-(2-amino-4-acetoxy-5- morpholinob enzoyl benzylamineN-ispropyl-N-(2-nitro-4-hydroxy 5 morpholinobenzoyl)benzylamine (10 g.)prepared as in Example 2 was heated for 3 hours with acetic anhydride(30 ml.) and acetic acid (30 ml.) to yield 11 g. of N-isopropyl-N-(2-nitro 4 acetoxy 5 morpholinobenzyl)benzylamine M.P. 118-120 C.

Catalytic hydrogenation of this nitro compound yieldedN-isopropyl-N-(2-amino-4-acetoxy 5 morpholinobenzoyl)benzylamine, M.P.118-120 C.

EXAMPLE 4 Preparation of N-isopropyl-N-(2-amino-4-ethoxyethoxy- 5-morpholinobenzoyl) benzylamine A solution ofN-isop-ropyl-N-(2-nitro-4-hydroxy 5- morpholinobenzyl)benzylamine (10g.) in acetone ml.) was reacted with ethyl fi-bromoethyl ether (10 g.)and anhydrous potassium carbonate (5 g. at 50 C. for 18 hours. Thereaction product, N-isopropyl-N-(Z-nitro-4-ethoxyethoxy-5-morpho1inobenzoyl)benzylamine, on reduction withhydrogen gave 8.0 g. of N-isopropyl-N-(Z- amino-4-ethoxyethoxy 5morpholinobenzoyl)benzylamine.

EXAMPLE 5 Preparation of N-sec-butylN(2-amino-4-chloro-5-hexamethyleneiminobenzoyl aniline Following the general procedureoutlined in Example 1, 2nitro-4,5-dichlorobenzoic acid (100 g.)(produced from the corresponding 2-nitro-4,5-dichlorotoluene byoxidation) was treated with thionyl chloride and the resulting acidchloride reacted with N-sec-butylaniline. The product yielded by thisreaction was 2-nitro-4,5-dich1oro- N-sec-butylbenzanilide, M.P. 109-112C.

2-nitro-4,S-dichloro-N-sec-buty1banzanilide (100 g.) was dissolved inhexamethyleneimine (1 liter) and the solution heated on a steam bath for15 hours, yielding 2- nitro-4-chloro-5-hexamethyleneimino Nsec-butylbenzanilide, M.P. 116-119 C.

To the 2-nitro-4-chloro-5-hexamethyleneimino-N-sec butylbenzanilide (100g.) was added acetic acid (500 hexamethyleneiminobenzyl)aniline having aM.P. between 64 and 67 C.

EXAMPLES 6-20 The preparation of other compounds of this invention maybe accomplished by substituting various other reac'tants in the generalpreparations set forth in Examples 1 through 5.

The following table sets forth additional compounds so produced. Thevarious substituents corresponding to the substituents shown in thegeneral formula are listed for each compound and the method ofpreparation that was followed in order to obtain the particular compoundis indicated.

6 EXAMPLES 21-40 Preparation of the diazonium metal salt complex fromeach of the substituted ortho-amino-benzylamines disclosed in the aboveexamples.

Fifty grams of the compound obtained from each of the Examples 1 through20 was dissolved in Water (74 ml.) and concentrated hydrochloric acid(75 ml.) and the solution cooled to 0 C. A 5-normal solution of sodiumnitrate was slowly added while maintaining the mixture at 0 to 10 C.until the response to Greens reagent gave a persistent positive result.To the cold solution was added 50% ZnCl solution precipitating the soliddiazo complex which was filtered off, washed and dried.

Other metal halides such as tin and cadmium chlorides and bromides canbe used instead of zinc chloride.

The diazonium cation may also be stabilized with reaction with mineralacid to form the diazonium sulfates and fiuoroborates.

Spectral examination of the diazotized compounds of Examples 21-25 gavepeak absorptions at 423, 430, 425, 425 and 410 millimicrons,respectively, and the absorption results of the remaining examplesappear in the table hereinabove presented.

Infrared Spectral CL Absorption Peak of i M r11 (1 r m Con-88' e o oazomum Example A B R1 R2 0" M.P., 0. Preparation Salt x 6 CHsO -N\-CHzCH(CHs)2 -CH2CH(CHs)z 91-93 Example1- 431 7 CH O N 0 IL 142 145 d 4s CHaO -N -N 112-115 do 420 9 CHsO 02 15 CeHs 119-123 ..do- 420 10 CHsON 0 118-120 do 418 --CH 0 11 (EH N -CHa 1 -63 .....do 41s 12 CHQO N N82-85 do 430 13 CH3O -N 'N 134435 do 422 CH 14 CHaO N 127-130 do. 425

15 CHsO I -CuH11 "CoHn 128-131 Example1 430 16 CHaO 0 -Ca 5 CoHa 163-167-..d0 425 17 CHaO -N CH(CHs)2 --CH2CoHs 102-105 -do 430 18 C4H9O -N 0OH(CHa)2 l -CH2CuH5 .1 Example 4-... 425

19 CsH OC2H4O -N 0 -C2H5 CeH5 ..d0 425 LJ 2O Chlorine -N -CH2CH(CHs)2-CH2CH(CHa)2 96-98 Example5- 425 7 EXAMPLE 41 The compound prepared inExample 26 was used to sensitize a base material, such as paper, byapplying the following sensitizing solution:

Water milliliters 1000 2 (N,N-diisobutylcarboxamido) 4hexamethyleneimino 5 methoxybenzenediazonium chloride ZnCl complex (0.03mole) grarns 20.0 Sodium 2,3 dihydroxynaphthalene 6 sulfonate grams 30.0

Thiourea do 50.0

Citric acid do 15.0

Zinc chloride do 60.0

The above solution was coated at the rate of 15 grams per square yard toproduce a two-component diazotype paper developable in an alkalinemedium (such as exposure to ammonia gas), enabling the azo-dye couplingreaction to proceed between the diazonium salt and the coupler, sodium2,3-dihydroxynaphthalene-6-sulfonate. A dense blue azo-dye image wasproduced.

EXAMPLE 42 The stabilized diazonium salt prepared in Example 28 from theamine produced in Example 8 was used to prepare a one-component paper asfollows.

Sensitizing solution:

Water milliliters 1000 2 (hexamethyleneiminocarbonyl) 4 piperidino 5methoxybenzenediazonium chloride SnCL; complex (0.03 mole) grams 12.0

Tartaric acid do 50.0 Developer:

Water milliliters 1000 Potassium tetraborate grams-.. 60.0 Potassiumhydroxide do 7.5 Phloroglucinol do 5.5 Resorcinol do 4.5

The above sensitizing solution was applied to a suitable base support atthe rate of 15 grams per square yard.

The light sensitive paper was exposed through a translucent ortransparent original to actinic radiation. A reproduction of theoriginal was then developed by applying the above developer solution tothe latent diazo image, producing a brown azo-dye image of suitabledensity.

EXAMPLE 43 Water milliliters 1000 Sodium benzoate "grams-.. 24.0 Sodiumcitrate ..d0 45.0 Sodium formate ..-do 12.0 Phloroglucinol do 8.0

A dense black azo-dye was produced with either diazonium salt.

It will be appreciated that the ability of the diazonium compoundsincorporated in sensitizing solutions and applied to a base support toundergo rapid photodecomposition, referred to in the art as printingspeed, is a most important property pertinent to its function as areproduction medium. The diazotype materials in the foregoing examplesare capable of much shorter periods of exposure than the diazotypematerials known heretofore. Property of greater printing speeds ismanifest when exposed to ultraviolet as well as visible light.

A comparative test of diazotype papers prepared with the diazonium saltsof this invention and those containing a prior art material,2,5-dibutoxy-4-morpholinobenzenel-diazonium chloride SnCl; complex, withthe same molar concentration of the sensitizing solutions, shows theformer to be much faster printing.

The comparison involved exposing the particular diazotype materialthrough a transparent original to both ultraviolet light and light inthe visible range under controlled conditions. The ultraviolet lightsource was a mercury vapor lamp rated at watts per lighted inch of lamp.The samples to be tested, together with the original, are moved past themercury light source at variable rates of speed in a controlled pathdirecting light onto the surface of the sheet from a fixed distance of 2inches. The greater the speed the less the time of exposure and hencethe exposure of the mercury lamp is reported in terms of feet per minutenecessary to produce a copy of proper contrast, i.e., maximumdecomposition in the background areas.

The response to visible light was measured with a 500- watt photofloodlamp operating in a 3400 K. color temperature which is manufactured byGeneral Electric Company. Exposure tests in visible radiation werecarried out at a distance of 3 inches and 6 inches from the sample.

The results of the tests are as follows:

U.V. Visible Light (seconds) Radiation (it/min) 3 in. 6 in.

Prior art; 44 5 8. 5 Example 41 material 76 2. 5 3. 5 Example 42material 76 2 3 Example 43 material 76 2 3 I claim:

1. The diazonium compound having one of the following general formulas:

in which X is an anion; wherein A is lower alkoxy, lower alkyl, loweracyloxy, hydroxy, halogen; B is pyrrolidinyl, piperizinyl, morpholinyl,piperidinyl, hexamethyleneirnine; R is lower alkyl, phenyl, cyclohexyl,and lower alkyl substituted furan; R is cyclohexyl, phenyl, phenylsubstituted lower alkyl, lower alkyl; and

in which X is an anion; wherein A is lower alkoxy, lower alkyl, loweracyloxy, hydroxy, halogen; B is pyrrolidinyl, piperizinyl, morpholinyl,piperidinyl hexamethyleneimine; R is lower alkyl, phenyl, cyclohexyl,and lower alkyl substituted furan; R is cyclohexyl, phenyl, phenylsubstituted lower alkyl, lower alkyl; and

is a. saturated cyclic amine residue selected from the group consistingof pyrrolidine, piperidine, lower alkyl substituted piperidine,hexamethyleneimine, -3-azabicyc1o (3.2.2)nonane, morpholine, and loweralkyl substituted morpholine.

7. The light-sensitive material described in claim 6 wherein thelight-sensitive compound is the double salt of stannic chloride of a2-N-(3-azabicyclo(3.2.2)nonylcarbonyl)-4-morpholindS-methoxybenzenediazonium compound.

8. The light-sensitive material described in claim 6 wherein thelight-sensitive compound is the double salt of stannic chloride of a2-(hexamethyleneiminocarbonyl)-4- piperidino-S-methoxy benzene diazoniumcompound.

9. The light-sensitive material described in claim 6 wherein thelight-sensitive compound is the double salt of zinc chloride of a2-(N,N-diisobutylcarboxamido)-4- hexamethyleneimino-S-methoxy benzenediazonium compound.

References Cited UNITED STATES PATENTS 8/1946 Sease et al. 96--75 8/1967 Hendrickx et a1. 96-91 OTHER REFERENCES NORMAN G. TORCHIN, PrimaryExaminer C. BOWERS, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,463,639 August 26, 1969 Evan S. Baltazzi It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:

Columns 5 and 6, in the table, heading of the last column, line 1thereof, cancel "Infrared".

Signed and sealed this 21st day of April 1970.

(SEAL) Attest:

Edwerd M. Fletcher, Jr. E.

Attesting Officer Commissioner of Patents

